JP2013195621A - Toner for electrostatic charge image development, two-component developer, and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent cleanability, improves transfer efficiency, eliminates image defects during respective transfer and outputs images with good reproducibility for a long period, and has low-temperature fixability and high storability under high temperature.SOLUTION: A toner for electrostatic charge image development includes inorganic fine particles as an external additive on the surface of toner base particles including at least a binder resin and a mold release agent. The toner base particles have the BET specific surface area of 2.5 m/g to 5.0 m/g; and the inorganic fine particles contains inorganic fine particles (A) in which at least a plurality of primary particles adhere to each other to form a second particle.

Description

  The present invention relates to a toner used as a developer, a two-component developer containing the toner, and an image using the toner when developing an electrostatic image formed by electrophotography, electrostatic recording, or the like. The present invention relates to a forming apparatus.

  The image forming apparatus includes a charging step for uniformly charging an image forming area on the surface of the image carrier, an exposure step for writing on the image carrier, a developing step for forming an image with toner frictionally charged on the image carrier, The image is fixed on the printing paper after a transfer process in which the image on the image carrier is transferred directly to the printing paper or indirectly via an intermediate transfer body. Further, the untransferred toner remaining without being transferred onto the image carrier is scraped off from the image carrier by the cleaning process, and enters the next image forming process.

  As the developer used, there are a two-component developer composed of a toner and a carrier and a one-component developer composed of only a magnetic or non-magnetic toner. The production of these toners is generally a kneading and pulverizing method in which a resin, a pigment, a charge control agent, and a release agent are melt-kneaded and cooled and then pulverized and classified. It is difficult to control.

Under such circumstances, recently, there has been an attempt to control the particle size of toner particles intentionally to solve the above-mentioned problems, and polymerized toner methods such as emulsion polymerization method and dissolution suspension method as aqueous granulation. Became popular.
In recent years, there has been an increasing demand for higher image quality, and in particular, in order to realize high-definition images in color image formation, there has also been an increasing demand for toner diameter reduction and particle size uniformity. When an image is formed using a toner having a wide particle size distribution, the problem that the fine powder toner contaminates the developing roller, charging roller, charging blade, photosensitive member, carrier, etc., or the toner scatters increases, resulting in high image quality. And it was difficult to achieve high reliability at the same time. On the other hand, when the particle size is uniform and the particle size distribution is sharp, the development behavior of the individual toner particles is uniform, and the reproducibility of minute dots is greatly improved.

As a fixing method in the electrophotographic method, a heating heat roller method in which a heating roller is directly pressed against a toner image on a recording medium and fixed is widely used from the viewpoint of energy efficiency. The heating heat roller system requires a large amount of power for fixing. Therefore, various studies have been made to reduce the power consumption of the heating roller from the viewpoint of energy saving. For example, a method is generally used in which the output of the heater for the heating roller is weakened when the image is not output and the output of the heater is increased to increase the temperature of the heating roller when the image is output.
However, in this case, in order to raise the temperature of the heating roller to the temperature necessary for fixing from the sleep time, a waiting time of about several tens of seconds is required, and this waiting time becomes a stress for the user. In addition, when the image is not output, it is desired to suppress power consumption by completely turning off the heater. In order to achieve these requirements, it is necessary to lower the fixing temperature of the toner itself and lower the fixing temperature of the toner when it can be used.

The toner used in the developer is required to have excellent low-temperature fixability, storage stability (blocking resistance), and stress resistance along with the development of electrophotographic technology. Various attempts have been made to use a polyester resin having a higher affinity with a recording medium or the like than a styrene resin that has been used and excellent in low-temperature fixability.
However, when designing a toner that places importance on low-temperature fixability, there is a trade-off relationship between storage stability and stress resistance due to softening of the resin, and both are necessary.

In order to solve these problems, a capsule structure composed of core particles containing a resin having a low glass transition temperature and an outer shell containing a resin having a high glass transition temperature formed so as to cover the surface of the core particles. Toners have been devised.
For example, a mixed liquid of a core constituent material containing a monomer (polymerizable monomer) that is a raw material of a thermoplastic resin and an outer shell constituent material containing amorphous polyester is dispersed in a dispersion medium. There has been proposed a capsule toner in which an outer shell is formed by an in-situ polymerization method in which the outer shell constituent material is unevenly distributed on the surface of the droplet as the core particles are formed by polymerization (see Patent Document 1).

Further, by adding an aqueous dispersion of resin fine particles obtained by emulsion polymerization or soap-free emulsion polymerization to polymer particles (core particles) obtained by suspension polymerization, 95% or more of the surface of the polymer particles is obtained. There has been proposed a toner which is coated with fine particles and then heated to a temperature higher than the glass transition temperature of the polymer particles so as to have a surface substantially free of bulges (see Patent Document 2).
Also, a coating resin is provided by mixing at least two kinds of resin fine particles having different glass transition temperatures and a toner core material (core particle), and fixing or fusing the resin particles on the toner core material while raising the temperature. Toner has been proposed (see Patent Document 3).
Further, the surface of a core toner (core particle) made of a binder resin having an average particle diameter of 2 to 20 μm and a glass transition temperature of 30 to 55 ° C. is coated or fixed or fused with a resin fine particle encapsulating wax. There has been proposed a toner obtained by a process including a first stage process to be performed and a second stage process in which resin fine particles not containing wax are coated and fixed or fused (see Patent Document 4).
However, although the above-mentioned patent documents can improve the problems of storage stability, blocking resistance and cohesiveness at high temperatures, no countermeasures are taken against stress in the development process, and toner deterioration due to development stress. In addition, there is a concern that transferability, developability, and cleaning properties may be deteriorated due to this.

In order to improve these transfer properties, developability and cleaning properties, Patent Document 5 discloses that medium-sized inorganic fine particles having an average particle size of 20 to 40 μm are used in combination with external additives.
Further, it is disclosed that inorganic fine particles having a large particle diameter are used in order to suppress burying of the external additive due to stress in the developing machine (see Patent Documents 6 to 8).
Initially, good cleaning properties, transferability, and developability can be obtained, but the adhesion of inorganic fine particles is non-uniform for each particle, and the inorganic fine particles are released over time, so that the inside of the developing machine or photosensitive Contamination around the body and sufficient transfer and cleaning properties may not be obtained.

  In contrast, as a means for reducing the non-electrostatic adhesion between the toner particles and the electrophotographic photosensitive member, or between the toner particles and the intermediate transfer member, the type and amount of the additive are adjusted (especially addition with a large particle size). Have been proposed (see Patent Document 9). By this method, the toner particles can obtain the effect of reducing the non-electrostatic adhesion force and improve the transfer efficiency, and also can obtain the effects of improving the development stability and cleaning.

  Furthermore, with the recent reduction in toner particle size and toner particle shape control, the amount of external additive added has increased, causing problems such as filming and carrier contamination. In addition, even if a high-quality image can be output initially, if the shape of the toner particles is complex, the quality of the toner particles is increased over time due to the external additive being buried or rolling of the external additive into the recess. It is difficult to maintain a correct image. In particular, when the fine uneven structure on the toner surface becomes large, the loss of the external additive function due to burying or rolling of the external additive becomes large. In addition, when an additive having a large particle size is added, the effect of improving the fluidity of the toner is small, which may affect the replenishability of the toner.

  The toner particles described above can initially improve the transfer efficiency of the image forming apparatus. However, the toner is subjected to mechanical stress such as stirring for a long time in the developing device of the image forming apparatus. Then, the additive is buried in the toner base or rolls into a recess on the surface of the toner base, and the effect of reducing the adhesive force by the additive is not exhibited, and the transfer efficiency of the image forming apparatus is lowered. . Particularly in the case of a high-speed machine, since the stirring in the developing device is intense, this mechanical stress is large, and the embedding of the additive in the toner base is easily accelerated. For this reason, it is assumed that transfer efficiency is lowered at a relatively early stage. In recent years, it has been disclosed that the use of an external additive having a relatively large particle size suppresses burying. However, as described above, the effect of imparting toner fluidity is low and the free external additive causes filming. There is a problem.

  For this reason, in order to maintain high transfer efficiency stably over a long period of time on a high-speed machine, the surface properties of the toner must be such that the additive can be present on the surface without being embedded in the toner base even under mechanical stress. It is necessary to control (mechanical strength). Furthermore, if the surface property (mechanical strength) of the toner is too strong (hard), the toner melts during fixing, or in the case of a toner containing a release agent such as wax, a fixing roller during fixing. It is also necessary to pay attention to the side effect that the release of the release agent to the ink becomes insufficient and the fixing property deteriorates. Furthermore, a high transfer rate can be maintained by simply spheroidizing the toner, but there is a side effect that the cleaning property of the toner is deteriorated.

  A method of introducing crystalline polyester by a polymerization method for the purpose of improving low-temperature fixability is also disclosed. As a method for preparing a dispersion of crystalline polyester, Patent Document 6 discloses a method for preparing a dispersion using a phase separation solvent. Although low-temperature fixability can be achieved by using crystalline polyester, The toner using the conductive polyester is not sufficient because the external additive tends to be buried and the transfer efficiency tends to decrease.

  In addition, it is disclosed that a non-spherical external additive is used to improve image density stability (Patent Documents 10 and 11). The transfer efficiency can be improved by the non-spherical external additive. However, when non-spherical fine particle aggregates are present, the amount of adhesion to the toner decreases, and the aggregate of the free non-spherical fine particles reduces the aggressiveness to the photoreceptor. There is no mention of the problem of the occurrence of defects such as increasing and generating photoconductor scratches.

  That is, in recent years, spherical toner having a small particle diameter has been developed by aqueous granulation, but there remains a problem in cleaning properties. By making the toner base particles have a high BET specific surface area, the unevenness of the surface becomes large, which is superior in cleaning properties. In addition, since the effective coverage of the external additive is lowered, it is also effective for low-temperature fixability. However, the toner with a high specific surface area of the toner has the effect of the external additive under stress such as rolling of the external additive into the concave part due to stress and embedding of the external additive in the convex part due to the unevenness. There were many things that could not be demonstrated.

An object of the present invention is to provide a toner that solves the above-described conventional problems.
That is, the object of the present invention is to provide a toner obtained from toner particles having a high BET specific surface area, so that the effect of the external additive can be sufficiently exerted even under stress, excellent cleaning properties, and improved transfer efficiency. It is an object to provide a toner that eliminates image defects during transfer and outputs an image with good reproducibility in the long term, and has low-temperature fixability and high storage stability at high temperatures.

The above problems are solved by (1) to (10) of the present invention.
(1) An electrostatic charge image developing toner having inorganic fine particles as external additives on the surface of toner base particles having at least a binder resin and a release agent, wherein the toner base particles have a BET specific surface area of 2. a 5m ² /g~5.0m ² / g, the inorganic fine particles are static, characterized by containing the inorganic fine particles (a) at least primary particles to form a plurality coalesced by the secondary particles Toner for charge image development.
(2) the toner according to (1) BET specific surface area is characterized by a 3.5m ² /g~5.0m ² / g of toner base particles.
(3) When the particle diameter of the 50% measured from the small particle side of the secondary particle diameter Db of the inorganic fine particles (A) is Db50 and the particle diameter of the 10% measured from the small particle side is Db10, Db50 / Db10 is 1.20 or less, The electrostatic image developing toner according to (1) or (2) above.
(4) When the secondary particle diameter of the inorganic fine particles (A) is Db, the average primary particle diameter of a plurality of primary particles forming the secondary particles is Da, and the degree of adhesion G is Db / Da, The toner for developing an electrostatic charge image according to any one of (1) to (3), wherein an average value of the degree of coalescence G is 1.5 to 4.0.
(5) The electrostatic charge image according to any one of (1) to (4), wherein the inorganic fine particles (A) contain 10% by number or less of particles having an adhesion degree G of less than 1.3. Development toner.
(6) The electrostatic image developing toner according to any one of (1) to (5), wherein the inorganic fine particles (A) have an average secondary particle diameter Dba in the range of 80 nm to 200 nm. .
(7) The electrostatic image developing toner according to any one of (1) to (6), wherein the toner is granulated in an aqueous medium.
(8) The toner is obtained by dispersing an oil phase obtained by dissolving or dispersing a toner material containing at least a polyester resin, a colorant, and a release agent in an organic solvent in an aqueous medium to obtain an emulsified dispersion. The toner for developing an electrostatic charge image according to any one of (1) to (7), which is obtained by removing an organic solvent from the emulsified dispersion.
(9) A two-component developer comprising the electrostatic image developing toner according to any one of (1) to (8).
(10) An image forming apparatus using the toner for developing an electrostatic image according to any one of (1) to (8).

  According to the present invention, it is excellent in cleaning properties, improves transfer efficiency, eliminates image defects at the time of each transfer, outputs an image with good reproducibility in the long term, and has low temperature fixability and high storage stability at high temperatures. The toner can be provided.

It is a schematic explanatory drawing which shows an example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. It is a schematic explanatory drawing which shows the other example of the image forming apparatus used by this invention. FIG. 4 is a schematic explanatory view showing a part of the image forming apparatus shown in FIG. 3. It is a FE-SEM image of the inorganic particle (A) which is the external additive of the toner of the present invention, and the arrow indicates the secondary particle diameter. It is an inorganic particle (A) FE-SEM image which is an external additive of the toner of the present invention, and an arrow indicates a primary particle diameter.

The toner for developing an electrostatic charge image of the present invention has inorganic fine particles as external additives on the surface of toner base particles having at least a binder resin and a release agent, and the toner base particles have a BET specific surface area of 2.5 m. ² / g to 5.0 m ² / g, and the inorganic fine particles contain inorganic fine particles (A) in which a plurality of primary particles are combined to form secondary particles.

  The toner of the present invention having the above-described characteristics suppresses the embedding of the external additive and the movement to the concave portion, which are expected to occur when the toner is subjected to stress such as being stirred in the developing device. Thus, it is possible to maintain a high transfer rate over time. Further, high cleaning properties due to the unevenness of the toner surface are ensured, and at the same time, the effective coverage of the external additive is lowered, so that the effect of significantly acting on the low temperature fixability is exhibited.

Usually, in the electrophotographic image forming apparatus, when a small particle size toner is used, the non-electrostatic adhesion force between the toner particles and the electrophotographic photosensitive member or between the toner particles and the intermediate transfer member is increased. The transfer efficiency is further reduced. In particular, when a small-diameter toner is used in a high-speed machine, non-electrostatic adhesion to the intermediate transfer member is increased by reducing the particle diameter of the toner, and the transfer nip portion, It is known that the transfer efficiency in the secondary transfer is significantly reduced because the time during which the toner particles are subjected to the transfer electric field in the nip portion of the secondary transfer is shortened.
However, in the toner of the present invention, the non-electrostatic adhesion force of the toner particles is reduced by reducing the embedding of the external additive in the toner base, and the transfer time is shortened as in a high-speed machine. However, sufficient transfer efficiency can be obtained. In addition, even when the mechanical stress over time is large as in a high-speed machine, the external additive itself is difficult to roll, so the external additive does not roll into the toner recess and the function of the external additive is not lost. In particular, it is possible to maintain a sufficient transfer efficiency. This eliminates the need for the toner base to have a low BET specific surface area in order to prevent the external additive from rolling and to secure fluidity, and at the same time, can increase the BET specific surface area. The additive coverage can be lowered, and the low-temperature fixability can be made superior. Furthermore, since the effect of consent can be expected to increase the degree of modification, long-term cleaning properties can be ensured.

BET specific surface area of the toner base particles according to the present invention is required to be 2.5m ² /g~5.0m ² / g, ranging in particular from 3.0 m ² / g of 4.0 m ² / g Is preferred. When this is smaller than 2.5 m ² / g, the BET specific surface area is low, so the external additive is easily embedded in the base material, and high transferability cannot be maintained, or the effective coverage of the external additive is increased. Therefore, there is a concern that the low-temperature fixability may be hindered. On the other hand, if it exceeds 5.0 m ² / g, the degree of deformation is too high, and the effective coverage as an additive becomes too low, so there is a concern about adverse effects on storage stability.
The BET specific surface area of the toner base particles can be adjusted by, for example, the mixing time and the aging temperature after adding the aqueous medium when manufacturing the toner base particles in the preferable toner manufacturing method described later. For example, by extending the mixing time after adding the aqueous medium, coalescence (convergence) of the emulsified particles proceeds and the surface irregularities are reduced. Further, since the surface of the binder resin itself is tanned by raising the aging temperature, the surface becomes smooth with no irregularities.

  The inorganic fine particles (A) preferably have a Db50 / Db10 of 1.20 or less, particularly 1.15 or less in the particle size distribution of the secondary particle diameter Db. Here, Db50 represents the 50% particle diameter measured from the small particle side of the secondary particle diameter observed by the FE-SEM, and Db10 represents the 10% particle diameter measured from the small particle side. Db50 / Db10 indicates the ratio of small particles having a secondary particle size and center particle, and an increase in this value indicates that there are many particles having a small secondary particle size. That is, either the particle A existing in the state of primary particles in which coalescence has not progressed, or the coalescence has progressed, but the primary particles themselves have many particles B having a small particle diameter, or both. It means that. Such particles A or B do not have sufficient functions. The particle A cannot function as an irregular additive and is inferior in embedment resistance, so there is a concern that an abnormal image may be generated. On the other hand, B cannot function as a spacer effect, and is buried due to external stress. There is a high possibility that it cannot be suppressed. It is desirable to reduce these particles, that is, Db10 is large. When Db50 / Db10 exceeds 1.2, the number of the above-described particles A and B is too large, so that it is difficult to perform the function as a deformed additive characterized for suppressing burial.

  Moreover, it is preferable that the average value of the adhesion degree G exists in the range of 1.5-4.0, and the range of 2.0-3.0 is especially preferable. When this is smaller than 1.5, the external additive tends to be buried in the base material, and the function of maintaining high transferability tends to be slightly inferior, for example, because the external additive tends to roll into the recess. On the other hand, when the ratio is larger than 4.0, the external additive is easily peeled off from the toner, and carrier contamination and the photoconductor are easily damaged.

In addition, it is preferable that the number of the inorganic fine particles having the above-mentioned adhesion degree G of less than 1.3 is 10% by number or less. The degree of coalescence G has a distribution in production, and particles having a degree of coalescence of less than 1.3 are particles that have not undergone coalescence, and are present in a nearly spherical state. For this reason, it is difficult to perform the function as a variant additive characterized for suppressing burial.
The average secondary particle diameter Dba of the fused silica is preferably in the range of 80 nm to 200 nm, and particularly preferably in the range of 100 nm to 160 nm. If it is less than 80 nm, it is difficult to perform the function of the spacer effect, and it is difficult to suppress burying due to external stress. On the other hand, if it exceeds 200 nm, release from the toner tends to occur, and photoconductor filming tends to occur.

  The toner of the present invention is preferably a toner that is granulated in an aqueous medium. A toner material containing at least a polyester resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent. A toner obtained by dispersing the obtained oil phase in an aqueous medium to obtain an emulsified dispersion and removing the organic solvent from the emulsified dispersion is more preferable. Particularly preferably, it is obtained by dissolving or dispersing a toner material containing at least an active hydrogen group-containing compound, a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound, a polyester resin, a colorant, and a release agent. A toner obtained by dispersing an obtained oil phase in an aqueous medium to obtain an emulsified dispersion, reacting the binder resin precursor with the active hydrogen group-containing compound in the emulsified dispersion, and removing the organic solvent It is.

[Toner characteristics measurement method]
<Toner base BET specific surface area measurement>
The BET specific surface area of the toner was measured using an automatic specific surface area / pore distribution measuring apparatus Tri Star 3000 (manufactured by Shimadzu Corporation).
1 g of toner was put in a dedicated cell, and degassing treatment was performed in the dedicated cell using a Tri Star degassing unit, Bacuprep 061 (manufactured by Shimadzu Corporation).
The deaeration treatment was performed at room temperature, and was performed for 20 hours under a reduced pressure condition of at least 100 mtorr.
The dedicated cell that has been deaerated can automatically obtain the BET specific surface area using Tri Star 3000.
The adsorption gas was nitrogen gas.

[Method for measuring properties of inorganic fine particles]
<Measurement of adhesion degree>
The measurement of the degree of adhesion is obtained by image observation. After the inorganic fine particles (A) are dispersed in an appropriate solvent (such as THF), a sample obtained by removing the solvent on the substrate and drying it is observed with an FE-SEM. The secondary particle diameter of the inorganic fine particles (A) in the visual field is measured at an acceleration voltage of 5 to 8 kV and an observation magnification of 8 to 10 k times. Secondary particle size measures the longest length of aggregated particles. An example is shown in FIG.
Similarly, the primary particle diameter is observed with FE-SEM. The embedded whole image is predicted from the outer frame of the bonded inorganic fine particles (A), and the longest length of the whole image is measured. An example is shown in FIG. The average value of the secondary particle diameter of one inorganic fine particle (A) and the primary particle diameter of a plurality of primary particles bonded to the inorganic fine particle is determined to determine the degree of bonding.
Degree of coalescence = secondary particle diameter / average primary particle diameter 100 or more inorganic fine particles (A) were observed, the degree of coalescence of each particle was determined, and the average value of the degree of coalescence and the degree of coalescence were 1. Find the ratio less than .3.
By the measurement method described above, the particle size distribution of the secondary particle diameter is obtained, and Db50 and Db10 are calculated.

Hereinafter, an example of a method for producing the toner of the present invention will be specifically described.
The present invention is not limited to the toner production method exemplified here.
In emulsification or dispersion, it is preferable to use a dispersant from the viewpoint of stabilizing the oil droplets and sharpening the particle size distribution while obtaining a desired shape, if necessary. There is no restriction | limiting in particular as a dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. can be used. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable. Further, after removing the organic solvent, inorganic fine particles are externally added in the step of externally adding and mixing the additives.

[Raw materials used in the production of the toner of the present invention]
(Binder Resin: For convenience of explanation, the binder resin to the magnetic material described below may be referred to as toner material.)
The binder resin used in the method for producing the toner of the present invention is not particularly limited, and preferably contains at least two kinds of resins, such as polyester resins, silicone resins, styrene / acryl resins, styrene resins, acrylic resins, Known binder resins such as epoxy resins, diene resins, phenol resins, terpene resins, coumarin resins, amideimide resins, butyral resins, urethane resins, ethylene / vinyl acetate resins can be used.
Among them, the resin phase for the toner production method of the present invention is preferably a polyester resin that has sufficient flexibility even when the molecular weight is lowered, in that it can sharply melt during fixing and smooth the image surface. Further, other resins may be used in combination with the polyester resin.
The polyester resin used in the present invention is one or two or more polyols represented by the following general formula (1):
A- (OH) m (1)
[Wherein, A represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. m represents an integer of 2 to 4. ]
One or two or more polycarboxylic acids represented by the following general formula (2) are polyesterified.
B- (COOH) n (2)
[Wherein, B represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. n represents an integer of 2 to 4. ]

  Specific polyols represented by the general formula (1) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2, 3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl Propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide addition Products, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like.

  Specific polycarboxylic acids represented by the general formula (2) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid. Azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, Isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5 -Hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxyprop 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, Examples include butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and ethylene glycol bis (trimellitic acid).

(Crystalline polyester resin)
A crystalline polyester resin can be contained as the polyester resin.
Examples of the crystalline polyester resin include saturated aliphatic diol compounds having 2 to 12 carbon atoms as alcohol components, particularly 1,4-butanediol, 1,6-hexanediol, 1, -8 octanediol, 1,10- Decanediol, 1,12 dodecanediol, and derivatives thereof, and a dicarboxylic acid having 2 to 12 carbon atoms having at least a double bond (C═C bond) as an acidic component, or a saturated dicarboxylic acid having 2 to 12 carbon atoms, Especially synthesized using fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1, -8 octanedioic acid, 1,10-decanedioic acid, 1,12 dodecanedioic acid and their derivatives. Preferred are crystalline polyesters.

  Among them, in particular, 1,4-butanediol, 1,6-hexanediol, 1, -8 octanediol, 1,10-decanediol, 1,12 in that the difference between the endothermic peak temperature and the endothermic shoulder temperature is further reduced. Any one kind of alcohol component of dodecanediol, fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1, -8 octanedioic acid, 1,10-decanedioic acid, 1,12 -It is preferably composed of only one kind of dicarboxylic acid component of dodecanedioic acid.

  In addition, as a method for controlling the crystallinity and softening point of the crystalline polyester resin, a trivalent or higher polyhydric alcohol such as glycerin as an alcohol component and a trivalent or higher polyvalent such as trimellitic anhydride as an acid component can be used during polyester synthesis. Examples thereof include a method of designing and using a non-linear polyester that has been subjected to condensation polymerization by adding a polyvalent carboxylic acid.

The molecular structure of the crystalline polyester resin of the present invention can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. In the above, an example is one having absorption at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ based on δCH (out-of-plane variable angular vibration) of the olefin.

(Non-crystalline polyester resin)
In the present invention, an amorphous unmodified polyester resin can be used as the binder resin component. It is preferable that at least a part of the modified polyester resin obtained by crosslinking and / or elongation reaction of the binder resin precursor made of the modified polyester resin is compatible with the unmodified polyester resin. Thereby, low temperature fixability and hot offset resistance can be improved. For this reason, it is preferable that the polyol and polycarboxylic acid of the modified polyester resin and the unmodified polyester resin have similar compositions. Further, as the unmodified polyester resin, the non-modified polyester resin used in the crystalline polyester dispersion can also be used as long as it is unmodified.

  The acid value of the unmodified polyester resin is usually 1 to 50 KOHmg / g, preferably 5 to 30 KOHmg / g. Thereby, since the acid value is 1 KOHmg / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved at the time of fixing on the paper, and the low-temperature fixability can be improved. . However, if the acid value exceeds 50 KOHmg / g, the charging stability, particularly the charging stability against environmental fluctuations, may be reduced. In the present invention, the unmodified polyester resin preferably has an acid value of 1 to 50 KOHmg / g.

The hydroxyl value of the unmodified polyester resin is preferably 5 KOHmg / g or more. The hydroxyl value is measured using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1-2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, acetic anhydride is decomposed by adding water and shaking. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 ml of toluene and 30 ml of ethanol is used.

At this time, the measurement conditions are as follows.
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potentialial No
Stop for revaluation No

The urea-modified polyester resin can be used in combination with a polyester resin modified with a chemical bond other than a urea bond, for example, a polyester resin modified with a urethane bond, in addition to an unmodified polyester resin.
When the toner composition contains a modified polyester resin such as a urea-modified polyester resin, the modified polyester resin can be produced by a one-shot method or the like.

As an example, a method for producing a urea-modified polyester resin will be described.
First, a polyol and a polycarboxylic acid are heated to 150 to 280 ° C. in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin oxide, and if necessary, water generated while removing pressure is removed to have a hydroxyl group. A polyester resin is obtained. Next, a polyester resin having a hydroxyl group is reacted with polyisocyanate at 40 to 140 ° C. to obtain a polyester prepolymer having an isocyanate group. Furthermore, the polyester prepolymer having an isocyanate group is reacted with amines at 0 to 140 ° C. to obtain a urea-modified polyester resin.

The number average molecular weight of the urea-modified polyester resin is usually 1000 to 10000, preferably 1500 to 6000.
In addition, when making the polyester resin which has a hydroxyl group and polyisocyanate react, and when making the polyester prepolymer which has an isocyanate group, and amines react, a solvent can also be used as needed.

Solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers (tetrahydrofuran) And the like which are inert with respect to the isocyanate group.
In addition, when using unmodified polyester resin together, you may mix to the solution after reaction of the urea modified polyester resin what was manufactured similarly to the polyester resin which has a hydroxyl group.

  In the present invention, as the binder resin component contained in the oil phase, a crystalline polyester resin, an amorphous polyester resin, a binder resin precursor, and an unmodified resin may be used in combination. The binder resin component may be contained. The binder resin component preferably contains a polyester resin, and more preferably contains 50% by mass or more of the polyester resin. When the content of the polyester resin is less than 50% by mass, the low-temperature fixability may be lowered. It is particularly preferable that all of the binder resin components are polyester resins.

  Examples of binder resin components other than polyester resins include polystyrene, poly (p-chlorostyrene), styrene-substituted polymers such as polyvinyltoluene, styrene-substituted polymers, styrene-p-chlorostyrene copolymers, and styrene-propylene copolymers. Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer , Styrene-vinyl methyl ketone copolymer Styrene copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; Methyl acid, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like.

(Binder resin precursor having a site capable of reacting with an active hydrogen group-containing compound)
The binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound (hereinafter referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins and the like. For example, polyol resins, polyacrylic resins, polyester resins, epoxy resins, derivative resins thereof, and the like can be used. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting. In addition, these may be used individually by 1 type and may use 2 or more types together.

  The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, an acid chloride Group, and the like. These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable. Among prepolymers, it is easy to adjust the molecular weight of the polymer component, ensuring oil-free low-temperature fixing characteristics for dry toners, especially good release and fixing properties even without a release oil coating mechanism for the heating medium for fixing. In view of the capability, a urea bond-forming group-containing polyester resin (RMPE) is particularly preferable.

  As a urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the polyester resin (RMPE) is particularly preferably an isocyanate group-containing polyester prepolymer (A). The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), and Examples include those obtained by reacting an active hydrogen group-containing polyester resin with polyisocyanate (PIC). There is no restriction | limiting in particular as a polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol ( TO) and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, diol (DIO) alone or a mixture of diol (DIO) and a small amount of a trivalent or higher polyol (TO) is preferable. Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.

  As the alkylene glycol, those having 2 to 12 carbon atoms are preferable, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. It is done. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of bisphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols. Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trihydric or higher polyhydric aliphatic alcohol, a trihydric or higher polyphenol, an alkylene of a trihydric or higher polyphenol. And oxide adducts. Examples of the trivalent or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and the like. Examples of the trihydric or higher polyphenols include trisphenol bodies (such as Trisphenol PA manufactured by Honshu Chemical Industry Co., Ltd.), phenol novolacs, cresol novolacs, and the like. Examples of the alkylene oxide adduct of trihydric or higher polyphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to trihydric or higher polyphenols.
The mixing mass ratio (DIO: TO) of the diol (DIO) and the trihydric or higher polyol (TO) in the mixture of the diol (DIO) and the trihydric or higher polyol (TO) is 100: 0.01 to 10 Is preferable, and 100: 0.01-1 is more preferable.

  There is no restriction | limiting in particular as polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) And a mixture of trivalent or higher valent polycarboxylic acids. These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of dicarboxylic acid (DIC) and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.

  Examples of the dicarboxylic acid (DIC) include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like. Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. Moreover, as alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. Moreover, as aromatic dicarboxylic acid, a C8-C20 thing is preferable, for example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned. Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

  The trivalent or higher polycarboxylic acid (TC) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids. Moreover, as an aromatic polycarboxylic acid, a C9-C20 thing is preferable, for example, trimellitic acid, pyromellitic acid, etc. are mentioned.

  The polycarboxylic acid (PC) is selected from dicarboxylic acid (DIC), trivalent or higher polycarboxylic acid (TC), and a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid. These acid anhydrides or lower alkyl ester compounds can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

As a mixing mass ratio (DIC: TC) of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC) in a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), There is no restriction | limiting, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.
The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the hydroxyl group in the polyol (PO) [ OH] and the equivalent ratio ([OH] / [COOH]) of the carboxyl group [COOH] in the polycarboxylic acid (PC) are usually preferably 2/1 to 1/1, and 1.5 / The ratio is more preferably 1-1 / 1, and particularly preferably 1.3 / 1-1.02 / 1.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of a polyol (PO), Although it can select suitably according to the objective, 0.5-40 mass% is preferable, for example. -30 mass% is more preferable, and 2-20 mass% is especially preferable. This is because if the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. This is because the low temperature fixability may be deteriorated if the temperature exceeds.

There is no restriction | limiting in particular as polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3 -Methyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These may be used alone or in combination of two or more.

  As a mixing ratio when the polyisocyanate (PIC) is reacted with an active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin), an isocyanate group [NCO] in the polyisocyanate (PIC) and a hydroxyl group in the hydroxyl group-containing polyester resin [ The mixing equivalent ratio with [OH] ([NCO] / [OH]) is usually preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1. It is particularly preferably 1 to 1.5 / 1. This is because if the isocyanate group [NCO] exceeds 5, low-temperature fixability may deteriorate, and if it is less than 1, offset resistance may deteriorate.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable, 1-30 mass% is more preferable, and 2-20 mass% is further more preferable. This is because, when the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability, and exceeds 40% by mass. This is because the low-temperature fixability deteriorates.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable. This is because if the average number of isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with urea bond-forming groups is lowered, and the hot offset resistance is deteriorated.
The weight average molecular weight (Mw) of the binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound is a molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF) and is 3,000. -40,000 is preferable, and 4,000-30,000 is more preferable. This is because when the weight average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

The molecular weight distribution can be measured by gel permeation chromatography (GPC), for example, as follows. That is, first, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) was flowed as a column solvent at a flow rate of 1 ml / min to adjust the sample concentration to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a tetrahydrofuran sample solution of the resin. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Alternatively, Toyo Soda Kogyo's molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6. It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

(Other ingredients)
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, charge control agents, inorganic fine particles, fluidity improvers, cleaning improvers, magnetic properties, and the like. Materials, metal soaps, and the like.

(Coloring agent)
The colorant for the toner used in the present invention is not particularly limited and can be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), Cadmium yellow, Yellow iron oxide, Ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Sand, Red Zhu , Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Par Nent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Chi Indigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue Phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, Zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green Examples include lean gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular in content in the toner of a coloring agent, Although it can select suitably according to the objective, 1-15 mass% is preferable and 3-10 mass% is more preferable. When the content of the colorant is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion occurs in the toner, resulting in a reduction in the coloring power, and the toner. The electrical characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polyester, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate, polybutyl Methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic Examples thereof include hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene N-acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The master batch can be produced by mixing or kneading a resin for a master batch and a colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
There is no restriction | limiting in particular as a mold release agent, Although it can select suitably according to the objective, The low melting-point mold release agent whose melting | fusing point is 50-120 degreeC is preferable. The low melting point release agent, when dispersed with the resin, effectively acts as a release agent between the fixing roller and the toner interface, thereby preventing oilless (a release agent such as oil on the fixing roller). Even if it is not applied), the hot offset property is good.
Preferable examples of the release agent include waxes and waxes. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and microcrystalline And natural waxes such as petroleum waxes such as Petrolatum; In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate, poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of a polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as melting | fusing point of a mold release agent, Although it can select suitably according to the objective, 50-120 degreeC is preferable and 60-90 degreeC is more preferable. If the melting point is less than 50 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 120 ° C., a cold offset may easily occur during fixing at a low temperature. The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. When the melt viscosity is less than 5 cps, the releasability may be lowered, and when it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained. There is no restriction | limiting in particular as content in the said toner of a mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable. When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

(Charge control agent)
The charge control agent is not particularly limited and may be appropriately selected from known materials according to the purpose. For example, a nigrosine dye, a triphenylmethane dye, a chromium-containing metal complex dye, a molybdate chelate pigment, Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, metal salts of salicylic acid, And metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.

  A commercially available product may be used as the charge control agent. Examples of the commercially available product include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, bontron S-34 of a metal-containing azo dye, O-naphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 ( As mentioned above, Hoechst Co., Ltd.), LRA-901, LR-147 (Nippon Kabushiki Kaisha) which is a boron complex -Lit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  By selectively containing the charge control agent in the resin phase in the toner particle main body existing in the inner layer, the spent of the charge control agent on other members such as a photoreceptor and a carrier can be suppressed. In the toner manufacturing method of the present invention, the arrangement of the charge control agent may be designed relatively freely, and an arbitrary arrangement may be taken according to each image forming process.

  The content of the charge control agent with respect to the toner varies depending on the type of the resin, the presence or absence of the additive, the dispersion method, and the like, and cannot be generally specified. -10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content of the charge control agent is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, By reducing the effect, the electrostatic attraction force with the developing roller may increase, leading to a decrease in developer fluidity and a decrease in image density.

(Fluidity improver)
A fluidity improver is an agent that increases surface hydrophobicity by surface treatment and prevents deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, and a fluoride are used. Silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. Silica and titanium oxide are particularly preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

(Cleaning improver)
The cleaning property improving agent is an agent added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid, etc. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as metal salts, polymethyl methacrylate fine particles, and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

(Layered inorganic mineral)
If necessary, a layered inorganic mineral may be contained in the toner. A layered inorganic mineral refers to an inorganic mineral formed by overlapping layers having a thickness of several nanometers, and modifying with organic ions means introducing organic ions into ions existing between the layers. Specifically, it is described in JP-T-2003-515795, JP-T-2006-500605, and JP-T-2006-503313. This is called intercalation in a broad sense. As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By doing so, the hydrophilicity becomes high, and such a modified layered inorganic mineral becomes finer and deformed during the production of the toner, and is particularly present in the surface portion of the toner particle, and it functions as a charge control and also at low temperature fixing. To contribute. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 5% by mass.

  The modified layered inorganic mineral used in the present invention is preferably a layered smectite-based basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

  Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates, or phosphates having A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 5% by mass.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Examples include quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Further, as the layered inorganic mineral partially modified with an organic anion, a layer modified with an organic anion represented by the following general formula (3) in DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) is particularly preferable. The following general formula (3) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
R ₁ (OR ₂ ) nOSO ₃ M: General formula (3)
[Wherein, R ₁ represents an alkyl group having 13 carbon atoms, and R ₂ represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

  By using the modified layered inorganic mineral, it has moderate hydrophobicity, and the oil phase containing the toner composition has a non-Newtonian viscosity in the production process of the toner having this, and the toner can be deformed.

(Inorganic fine particles)
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles. It is important that the inorganic fine particles contain inorganic fine particles (A) in which a plurality of primary particles are fused to form secondary particles. Thus, as the inorganic fine particles (A), the following fused silica is preferable. In addition, inorganic fine particles that can be appropriately selected from known ones according to the purpose, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide , Silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Can be used together. An inorganic fine particle (A) may be used individually by 1 type, and may use 2 or more types together.

The fused silica is referred to as fused silica by chemically agglomerating primary particles of silica and / or fused silica with a treating agent to cause secondary aggregation.
The fused silica used in the present invention is prepared by chemically bonding primary particles of crystalline silica and / or fused silica using a treating agent. Examples of the treating agent include alkoxysilanes and silane coupling agents. Silane type processing agents such as chlorosilanes and silazanes or epoxy type processing agents such as liquid epoxy resins are preferably used.
When the silica primary particles are treated with a silane treatment agent such as alkoxysilanes or silane coupling agents, silanol groups bonded to the silica primary particles react with alkoxy groups bonded to the silane treatment agent. A new Si—O—Si bond is formed by dealcoholization.

That is, as shown in the following formula, the silica primary particles are secondarily aggregated by chemical bonding via the silane-based treatment agent.

When the silica primary particles are treated with chlorosilanes, the chloro group of the chlorosilanes and the silanol group bonded to the silica primary particles form a new Si-O-Si bond by the dehydrochlorination reaction. When coexisting with water, chlorosilanes first hydrolyze into water to form silanol groups, and the silanol groups and the silanol groups bonded to the silica primary particles are each subjected to a new Si-O-Si bond by a dehydration reaction. To produce secondary agglomeration.
Silazanes form a new Si—O—Si bond and secondary agglomerate when the amino group and the silanol group bonded to the silica primary particles are deammoniated.

On the other hand, when silica primary particles are treated with an epoxy-based treatment agent, silanol groups bonded to the silica primary particles add an epoxy group oxygen atom of the epoxy-based treatment agent and a carbon atom bonded to the epoxy group. Then, a new Si—O—C bond is formed.
That is, as shown in the following formula, the silica primary particles are secondarily aggregated by a chemical bond via an epoxy-based treatment agent.

  The fused silica used in the present invention is prepared by preparing silica as primary particles, and then preparing fused silica by treating the silica with the above-described silane-based treatment agent or epoxy-based treatment agent to fill the epoxy resin. However, for example, when silica is synthesized by a sol-gel method, a fused silica may be prepared by a one-step reaction in the presence of the silane-based treatment agent or epoxy-based treatment agent.

  In addition, since the Si—O—Si bond to be produced is more stable to heat than the Si—O—C bond, the silane-based treatment agent is preferable to the epoxy-based treatment agent. . Specific examples of alkoxysilanes that are the silane-based treatment agents include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, Examples include methyldiethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane.

  Specific examples of the silane coupling agent that is the silane treatment agent include γ-aminopropyltoluethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane, and the like.

  Further, as silane-based treatment agents other than the above alkoxysilanes or silane-based coupling agents, specifically, vinyltrichlorosilane, dimethyldichlorosilane, methylvinyldichlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, N, Examples thereof include N′-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) acetamide, dimethyltrimethylsilylamine, hexamethyldisilazane, and cyclosilazane mixture.

  Specific examples of the epoxy-based treatment agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, biphenol type epoxy resin, Examples thereof include glycidylamine type epoxy resins and alicyclic epoxy resins.

The fused silica used in the present invention is prepared by chemically bonding primary particles of crystalline silica and / or fused silica using the above-mentioned treatment agent. The treatment is performed by first combining the primary silica particles and the treatment agent. The mixing is performed at a mass ratio of 100: 0.01 to 100: 50 using a known mixer such as a spray dryer.
At that time, for example, water or a 1% aqueous acetic acid solution may be appropriately added as a processing aid.
The mixture of the silica primary particles and the treating agent is then fired, and the firing temperature is selected from a temperature range of 100 to 2500 ° C.
The firing time may be 0.5 to 30 hours.

The degree of coalescence of silica can be arbitrarily controlled by adjusting the primary particle diameter, the type and amount of the treatment agent, and the treatment conditions.
That is, the cohesive strength is stronger when a silane-based treatment agent is used than when an epoxy-based treatment agent is used, when the amount of the treatment agent is increased with respect to primary silica particles, and when the firing temperature is higher. And the degree of adhesion tends to be high. On the other hand, the proportion of non-fused particles can be reduced by extending the firing time. However, excessive time extension promotes agglomeration of the coalesced particles, which may cause a problem in adhesion to the toner.

  The addition amount of the inorganic fine particles (A) is desirably 1.0 to 3.0 parts, more preferably 1.5 to 2.5 parts, with respect to 100 parts by mass (hereinafter, “parts”) of the toner. When the amount is less than 1.0 part, a sufficient spacer effect cannot be obtained and it is difficult to suppress burial due to external stress. On the other hand, if it is more than 3.0 parts, there is a concern that the amount of separation becomes large, which may cause defects such as photoconductor filming and chattering of the cleaning blade.

(Inorganic fine particles used in combination with inorganic fine particles (A))
The toner of the present invention may be used in combination with other inorganic fine particles in order to assist fluidity, developability and chargeability.
As the inorganic fine particles to be used in combination, the primary particle diameter is preferably 5 nm to 70 nm, and particularly preferably 5 nm to 50 nm. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

[Method for Producing Toner of the Present Invention]
The method for producing the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a pulverization method and a polymerization method such as an emulsion aggregation method and a dissolution suspension method. In order to obtain a toner having a small particle size and a small Dv / Dn, a dissolution suspension method is preferably used.

Specifically as each manufacturing method, it manufactures as follows.
The pulverization method is, for example, a method of obtaining the toner base particles by melting and kneading the toner material, pulverizing, classifying and the like.
In the case of the pulverization method, for the purpose of setting the average circularity of the toner in the range of 0.97 to 1.0, the shape is controlled by applying a mechanical impact force to the obtained toner base particles. May be.
In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.

Examples of the water-based granulated toner include an emulsion aggregation method and a dissolution suspension method, which are manufactured as follows.
<Emulsion aggregation method>
There is an emulsion polymerization aggregation method as a toner for granulating by dispersing and / or emulsifying an oil phase or a monomer phase containing at least a toner composition or a toner composition precursor in an aqueous medium.

  The emulsion polymerization agglomeration and fusion method comprises a resin particle dispersion prepared by an emulsion polymerization method, a layered inorganic mineral obtained by modifying at least a part prepared separately with organic ions, a colorant dispersion, and a release agent dispersion as necessary. A step of preparing an agglomerated particle dispersion (hereinafter referred to as “aggregation step”) by mixing and aggregating at least resin particles and a layered inorganic mineral at least partially modified with organic ions and a colorant to form aggregated particles. And a step of heating and coalescing the aggregated particles to form toner particles (hereinafter sometimes referred to as a “fusion step”).

  In the aggregating step, the resin particle dispersion, the layered inorganic mineral obtained by modifying at least a part of the organic ions, the colorant dispersion, and if necessary, the release agent dispersion are mixed with each other to aggregate the resin particles. To form agglomerated particles. Aggregated particles are formed by hetero-aggregation, etc., and at that time, for the purpose of stabilizing the aggregated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the aggregated particles or monovalent or more such as metal salt A compound having the following charge can be added. In the fusion step, the resin is melted by heating to a temperature equal to or higher than the glass transition point of the resin in the aggregated particles.

  In the previous stage of the fusing step, there can be provided an attaching step in which other fine particle dispersion is added to and mixed with the aggregated particle dispersion to uniformly attach the fine particles to the surface of the aggregated particles to form adhered particles. Furthermore, a layered inorganic mineral dispersion modified at least partly with organic ions is added to and mixed with the aggregated particle dispersion, and the layered inorganic mineral modified at least partly with organic ions is uniformly attached to the surface of the aggregated particles and adhered particles. An adhesion step for forming the film can be provided. Also, in order to strengthen the adhesion of layered inorganic minerals modified at least partly with organic ions, other fine particle dispersions are added after attaching layered inorganic minerals modified at least partly with organic ions An adhering step can be provided in which fine particles are uniformly adhered to the surface of the aggregated particles to form adhering particles. These adhered particles are formed by heteroaggregation or the like. Similarly to the above, this adhering particle dispersion is heated and fused to a temperature equal to or higher than the glass transition point of the resin particles to form fused particles.

  The fused particles fused in the fusion step exist as a colored fused particle dispersion in the aqueous medium, and at the same time the fused particles are taken out of the aqueous medium in the washing step, the impurities mixed in the respective steps are removed. The toner is removed and dried to obtain a toner for developing an electrostatic image as powder.

  In the washing step, acidic and possibly basic water is added in several times the amount to the fused particles and stirred, followed by filtration to obtain a solid content. The pure water is added several times to the solid content and stirred, followed by filtration. This is repeated several times until the pH of the filtrate after filtration reaches about 7, and colored toner particles are obtained. In the drying step, the toner particles obtained in the washing step are dried at a temperature below the glass transition point. At this time, it is possible to circulate dry air or heat under vacuum as necessary.

  Use a certain amount of surfactant if it is not always stable under basic conditions due to the stability of the colorant dispersion and release agent dispersion due to pH, etc., or because of the stability over time of the resin particle dispersion. Can do.

  Examples of such surfactants include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type And nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable. In the toner of the present invention, an anionic surfactant generally has a strong dispersing power and is excellent in the dispersibility of resin particles and a colorant. Therefore, a cationic agent is used as a surfactant for dispersing a release agent. Surfactants are advantageous. The nonionic surfactant is preferably used in combination with an anionic surfactant or a cationic surfactant. Surfactant may be used individually by 1 type and may use 2 or more types together.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate and other alkyl naphthalene sulfonate sodium, naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Sulfonates: lauryl phosphate, isopropyl phosphate, nonylphenyl ether phosphate Phosphoric acid esters such as Feto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate, sulfosuccinic acid salts, such as sodium lauryl sulfosuccinate 2; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bispolyoxyethylene methyl ammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkyltri And quaternary ammonium salts such as chill ammonium chloride.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Etc.

  The content of the surfactant in each dispersion may be a level that does not hinder the characteristics of the present invention, and is generally a small amount. Specifically, in the case of a resin particle dispersion, 0.01 to 1 mass. %, Preferably 0.02 to 0.5 mass%, more preferably 0.1 to 0.2 mass%. When the content is less than 0.01% by mass, aggregation may occur particularly when the pH of the resin particle dispersion is not sufficiently basic. The content in the case of the colorant dispersion and the release agent dispersion is 0.01 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.5 to 0.2% by mass. If the content is less than 0.01% by mass, the stability between the particles differs at the time of agglomeration, which causes problems such as the release of specific particles. If the content exceeds 10% by mass, the particle size distribution of the particles becomes wider. In addition, there are problems such as difficulty in controlling the particle diameter, which is not preferable.

In addition to the resin, colorant, and release agent, the toner of the present invention includes other components such as an internal additive, a charge control agent, inorganic particles, organic particles, a lubricant, and an abrasive depending on the purpose. It is possible to add the fine particles.
As an internal additive, it is used to such an extent that it does not hinder the chargeability as a toner characteristic. For example, a metal such as ferrite, magnetite, reduced iron, cobalt, manganese, nickel, an alloy, or a magnetic compound such as a compound containing these metals. The body is used.

  As described above, when the resin particle dispersion, the layered inorganic mineral dispersion modified at least partially with organic ions, the colorant dispersion, and the release agent dispersion are mixed, the content of the colorant is 50% by mass. It may be below, and the range of 2-40 mass% is preferable. The content of the layered inorganic mineral at least partially modified with organic ions is preferably in the range of 0.05 to 10% by mass. In addition, the content of other components only needs to be a level that does not hinder the object of the present invention, and is generally extremely small, specifically in the range of 0.01 to 5% by mass, A range of ˜2% by mass is preferred.

  In the present invention, as a dispersion medium for the resin particle dispersion, a layered inorganic mineral dispersion at least partially modified with organic ions, a colorant dispersion, a release agent dispersion, and a dispersion of other components, for example, an aqueous medium Is used. Specific examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  In the step of preparing the aggregated particle dispersion of the present invention, the aggregated particles can be adjusted by adjusting the emulsifying power of the emulsifier with pH to generate aggregation. At the same time, an aggregating agent may be added in order to stably and rapidly aggregate the particles to obtain aggregated particles having a narrower particle size distribution. As the flocculant, a compound having a monovalent or higher charge is preferable. Specifically, water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, Acids such as oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, sodium oxalate, phthalic acid Aliphatic acids such as sodium and potassium salicylates, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride and other aliphatic and aromatic amines Inorganic acid salts and the like. When considering the stability of the aggregated particles, the stability of the aggregating agent with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable in terms of performance and use.

  The amount of these flocculants to be added varies depending on the valence of the charge, but all of them are small amounts. The monovalent is 3% by mass or less, the divalent is 1% by mass or less, and the trivalent is 0. It is about 5% by mass or less. A smaller amount of the flocculant is preferable, and a compound having a higher valence is preferable because the amount added can be reduced.

<Dissolution suspension method>
In the toner production method of the present invention, a solution or dispersion formed by dissolving or dispersing a binder resin or a toner material mainly composed of a binder resin raw material and a colorant in an organic solvent is used as an aqueous medium. A desired toner is produced by emulsifying or dispersing in the mixture to prepare an emulsified or dispersed liquid. Preferably, a solution or dispersion of a toner material containing at least an active hydrogen group-containing compound and a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium. By reacting an active hydrogen group-containing compound with a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound in an aqueous medium, toner base particles containing at least an adhesive substrate are produced to produce desired toner particles. Produces toner.

(Dissolution or dispersion of toner material)
The solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in a solvent. The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. For example, the active hydrogen group-containing compound and a bond having a site capable of reacting with the active hydrogen group-containing compound are available. It contains any of the resin precursors (prepolymers), and may further contain other components such as an unmodified polyester resin, a release agent, a colorant, and a charge control agent, if necessary. The toner material dissolved or dispersed liquid is preferably prepared by dissolving or dispersing the toner material in an organic solvent. The organic solvent is preferably removed during or after the toner granulation.

(Organic solvent)
The organic solvent that dissolves or disperses the toner material is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. Preferred are those having a boiling point of less than 150 ° C. from the viewpoint of ease of removal, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform Monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like can be used. Further, ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as the usage-amount of an organic solvent, Although it can select suitably according to the objective, 40-300 mass parts is preferable with respect to 100 mass parts of toner materials, 60-140 mass parts is more preferable, 80 -120 mass parts is more preferable. The toner material is dissolved or dispersed in an organic solvent containing an active hydrogen group-containing compound, a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound, an unmodified polyester resin, and a release agent. In addition, toner materials such as a colorant and a charge control agent can be dissolved or dispersed. Further, in the toner material, components other than the binder resin precursor (prepolymer) having a site capable of reacting with the active hydrogen group-containing compound are added and mixed in the aqueous medium in the preparation of the aqueous medium described later. Alternatively, when the toner material dissolved or dispersed liquid is added to the aqueous medium, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

(Aqueous medium)
The aqueous medium is not particularly limited and can be appropriately selected from known ones. For example, water, a solvent miscible with water, a mixture thereof, and the like can be used. Is particularly preferred. The solvent miscible with water is not particularly limited as long as it is miscible with water. For example, alcohol, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, and the like can be used. Examples of the alcohol include methanol, isopropanol, and ethylene glycol. Examples of lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

(Emulsification or dispersion)
The dissolution or dispersion of the toner material in the aqueous medium is preferably carried out by dispersing the toner material dissolution or dispersion in the aqueous medium while stirring. There is no restriction | limiting in particular as a dispersion method, According to the objective, it can select suitably, For example, it can carry out using a well-known disperser etc. Examples of the disperser include a low speed shear disperser and a high speed shear disperser. In this toner manufacturing method, during emulsification or dispersion, an active hydrogen group-containing compound and a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a cross-linking reaction, thereby causing adhesion. A conductive substrate is produced.

(Adhesive substrate)
Adhesive base material exhibits adhesion to recording materials such as paper, and reacts an active hydrogen group-containing compound with a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound in an aqueous medium. It is preferable that the adhesive polymer formed is included. Note that a binder resin appropriately selected from known binder resins may be included. There is no restriction | limiting in particular as a weight average molecular weight of an adhesive base material, Although it can select suitably according to the objective, 3,000 or more are preferable, 5,000-1,000,000 are more preferable, 7, 000 to 500,000 is particularly preferred. This is because if the weight average molecular weight is less than 3,000, the hot offset resistance may deteriorate.

  There is no restriction | limiting in particular as glass transition temperature (Tg) of an adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. This is because if the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and if it exceeds 70 ° C., the low-temperature fixability may not be sufficient. In the electrophotographic toner of the present embodiment, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, good storability is exhibited even when the glass transition temperature is lower than that of a conventional polyester toner.

  The glass transition temperature (Tg) is measured by the following method using, for example, a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. To do.

  There is no restriction | limiting in particular as resin for adhesive base materials, Although it can select suitably according to the objective, A polyester-type resin etc. are especially suitable. There is no restriction | limiting in particular as a polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned as a particularly suitable thing. The urea-modified polyester resin includes an amine (B) as an active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound. Can be obtained by reacting in an aqueous medium. The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the content molar ratio of the urea bond and the urethane bond (urea bond / urethane bond) is not particularly limited and may be appropriately selected depending on the intended purpose, but is 100/0 to 10/90. Preferably, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable. This is because if the urea bond is less than 10, the hot offset resistance may be deteriorated.

Preferable specific examples of the urea-modified polyester resin include the following.
(1) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid Mixture with polycondensate (2) Polyester prepolymer obtained by reacting 2-condensate of bisphenol A ethylene oxide with polycondensate of isophthalic acid with isophorone diisocyanate and urea of bisphenol A ethylene oxide with 2 moles Mixtures with adducts and polycondensates of terephthalic acid

(3) Bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and a polyester prepolymer obtained by reacting a polycondensate of terephthalic acid with isophorone diisocyanate and urea compound with isophorone diamine, and bisphenol A ethylene Mixture of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate (4) bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and polycondensation of terephthalic acid A polyester prepolymer obtained by reacting a product with isophorone diisocyanate and uread with isophorone diamine, a 2-mole adduct of bisphenol A propylene oxide and terephthalic acid. A mixture of condensates

(5) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2-mole adduct, and terephthalate Mixture with acid polycondensate (6) Polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2-mole adduct and terephthalic acid polycondensate with isophorone diisocyanate and urethanized with hexamethylenediamine, and bisphenol A ethylene Mixture of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and polycondensate of terephthalic acid

(7) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate with urea and ethylenediamine 2 mol adduct and terephthalic acid Mixture with condensate (8) Polyester prepolymer obtained by reacting 2 mol of bisphenol A ethylene oxide adduct and isophthalic acid polycondensate with diphenylmethane diisocyanate and urea of hexamethylenediamine, and 2 mol of bisphenol A ethylene oxide Mixtures with adducts and polycondensates of isophthalic acid

(9) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate was uread with hexamethylenediamine. And a mixture of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate (10) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate A polyester prepolymer reacted with diisocyanate, uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid Compound

  The adhesive substrate (for example, urea-modified polyester resin) is obtained by, for example, (1) binding resin precursor (for example, isocyanate group-containing polyester prepolymer (A)) having a site capable of reacting with an active hydrogen group-containing compound. The dissolved or dispersed liquid of the toner material is emulsified or dispersed in an aqueous medium together with an active hydrogen group-containing compound (for example, amines (B)) to form oil droplets, and both are subjected to an extension reaction in the aqueous medium. Or (2) a solution or dispersion of the toner material is emulsified or dispersed in an aqueous medium to which an active hydrogen group-containing compound has been added in advance to form oil droplets. You may produce | generate by carrying out elongation reaction thru | or crosslinking reaction of both in a medium. Alternatively, (3) a toner material solution or dispersion is added and mixed in an aqueous medium, then an active hydrogen group-containing compound is added to form oil droplets, and both extend from the particle interface in the aqueous medium. It may be produced by a reaction or a crosslinking reaction. In the case of (3), the modified polyester resin is preferentially produced on the surface of the toner to be produced, and it becomes possible to provide a concentration gradient on the toner particles.

  Reaction conditions for producing an adhesive substrate by emulsification or dispersion are not particularly limited, and a combination of a binder resin precursor having a site capable of reacting with an active hydrogen group-containing compound and an active hydrogen group-containing compound. It can be selected as appropriate according to the conditions. In addition, as reaction time, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.

  In an aqueous medium, as a method for stably forming a dispersion containing a binder resin precursor (for example, an isocyanate group-containing polyester prepolymer (A)) having a site capable of reacting with an active hydrogen group-containing compound, for example, Binder resin precursor (for example, isocyanate group-containing polyester prepolymer (A)) having a site capable of reacting with an active hydrogen group-containing compound in an aqueous medium, colorant, release agent, charge control agent, unmodified polyester Examples thereof include a method of adding a toner material dissolved or dispersed by dissolving or dispersing a toner material such as a resin in an organic solvent, and dispersing the material by shearing force.

  In emulsification or dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material. This is because if the amount used is less than 50 parts by mass, the toner material is poorly dispersed and toner particles having a predetermined particle size may not be obtained. If the amount used exceeds 2,000 parts by mass, the production cost is high. Because it becomes.

  Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amide compounds Alternatively, homopolymers or copolymers such as those having methylol compounds, chlorides, nitrogen atoms or heterocyclic rings thereof, polyoxyethylenes, celluloses, and the like can be given. Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, Examples include glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like.

Examples of vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of esters of a compound containing vinyl alcohol and a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Moreover, as an amide compound or these methylol compounds, acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds etc. are mentioned, for example.
Examples of chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine.

Examples of the polyoxyethylene type include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples include ethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
When using a dispersion stabilizer that is soluble in acids and alkalis such as calcium phosphate, remove the calcium phosphate from the fine particles by dissolving the calcium phosphate with an acid such as hydrochloric acid and then washing with water or decomposing with an enzyme. It becomes possible to do.

(Anionic surfactant)
Examples of the anionic surfactant used in the production method of the present invention include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, etc., and an anionic surfactant having a fluoroalkyl group is preferable. It is mentioned in. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (having 6 to 6 carbon atoms). 11) Sodium oxy] -1-alkyl (C3-4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl ( Carbon number 11-20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) par -Fluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate and the like.

  Examples of commercially available anionic surfactants having a fluoroalkyl group include Surflon S-111, S-112, and S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 ( Dainippon Ink, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Etc.).

(Removal of organic solvent)
The organic solvent is removed from the emulsified slurry obtained by emulsification or dispersion. The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere, Examples thereof include a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation. When the organic solvent is removed, toner particles are formed. The formed toner particles are washed, dried, etc., and then classified as desired. The classification is performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like. The classification operation may be performed after obtaining the powder after drying.

The image forming apparatus of the present invention includes an electrostatic latent image forming process (charging process and exposure process), a developing process, a transfer process, a fixing process, and a cleaning process. You may further have processes, such as a process and a control process.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming unit preferably has a charger (charging unit) that uniformly charges the surface of the image carrier and an exposure unit (exposure unit) that exposes the surface of the image carrier.

Charging can be performed by applying a voltage to the surface of the image carrier using a charger. The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.
The exposure can be performed by exposing the surface of the image carrier using an exposure device. The exposure device can be appropriately selected according to the purpose, but various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be adopted.

  The development step is a step of forming a visible image by developing the electrostatic latent image using the toner of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing unit that accommodates the toner of the present invention and can apply the toner to the electrostatic latent image in a contact or non-contact manner. The developing device may be a dry development system or a wet development system. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used. The developer accommodated in the developing device is a developer using the toner of the present invention, but may be a one-component developer or a two-component developer.

  In a developing device having a two-component developer, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the image carrier.

The transfer step is a step of transferring a visible image to a recording medium. The intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the secondary transfer of the visible image onto the recording medium. It is preferable. At this time, the toner used may be monochrome, full color, or transparent toner. Usually, two or more colors are superimposed and developed at the same time. Therefore, a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer in which the composite transfer image is transferred onto a recording medium. It is more preferable to have a process.
The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.

  The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium can be appropriately selected from known recording media, and recording paper or the like can be used.

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be fixed each time the toner of each color is transferred to the recording medium, or each color toner is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. A known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization step is a step of neutralizing by applying a neutralization bias to the image carrier, and can be performed using a neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.

  The cleaning step is a step of removing toner remaining on the image carrier, and can be performed using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used. It is preferable to use a blade cleaner.

  A control process is a process of controlling each process, and can be performed using a control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  The process cartridge according to the present invention is used in the image forming apparatus of the present invention, and integrally supports an image carrier and at least one means selected from a charging means, a developing means, and a cleaning means, and the image of the present invention. It is detachable from the forming apparatus main body.

  FIG. 1 shows an example of an image forming apparatus used in the present invention. The image forming apparatus 100A includes a drum-shaped photosensitive member 10 as an additional carrier, a charging roller 20 as a charging unit, an exposure device 30 as an exposure unit, a developing device 40 as a developing unit, and an intermediate transfer member 50. And a cleaning device 60 as a cleaning means and a static elimination lamp 70 as a static elimination means.

  The intermediate transfer member 50 is an endless belt, and is stretched by three rollers 51 so as to be movable in the direction of the arrow. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. In addition, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) a visible image (toner image) to a recording sheet 95 serving as a recording medium is disposed to face the recording paper 95. . Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing device 45K, a yellow developing device 45Y, a magenta developing device 45M, and a cyan developing device 45C provided around the developing belt 41. The black developing device 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing device 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developer 45M includes a developer container 42M, a developer supply roller 43M, and a developer roller 44M. The cyan developer 45C includes a developer container 42C, the developer supply roller 43C, and a developer. A roller 44C is provided. The developing belt 41 is an endless belt, is stretched by a plurality of belt rollers so as to be movable in the direction of the arrow, and a part of the developing belt 41 is in contact with the photoreceptor 10.

  In the image forming apparatus 100A, the charging roller 20 uniformly charges the photoconductor 10, and then exposes the photoconductor 10 using the exposure device 30 to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoreceptor 10 is developed by supplying a developer from the developing device 40 to form a toner image. Further, the toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied by the roller 51, and further transferred (secondary transfer) onto the recording paper 95. As a result, a transfer image is formed on the recording paper 95. The toner remaining on the photoconductor 10 is removed by a cleaning device 60 having a cleaning blade, and the charged charge on the photoconductor 10 is removed by a static elimination lamp 70.

  FIG. 2 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100B does not include the developing belt 41, except that a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged around the photoconductor 10 so as to face each other. It has the same configuration as that of the image forming apparatus 100A and exhibits the same function and effect. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

FIG. 3 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus. The image forming apparatus 100 </ b> C includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder 400. The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16 so as to be able to move clockwise in the drawing. An intermediate transfer body cleaning device 17 for removing toner remaining on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched by the support rollers 14 and 15 is provided with a tandem developing device in which image forming means 18 of four colors of yellow, cyan, magenta, and black are opposed to each other along the conveying direction. 120 is arranged. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It is. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the image forming apparatus 100C, a sheet reversing device 28 for reversing the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Thereby, images can be formed on both sides of the recording paper.

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. First, a document is set on the document table 130 of the automatic document feeder 400, or the automatic document feeder 400 is opened to set a document on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed.
When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, after the original is conveyed onto the contact glass 32, on the other hand, when an original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, the reflected light from the original surface of the light irradiated by the first traveling body 33 is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35. As a result, a color original (color image) is read and used as image information for each color of black, yellow, magenta, and cyan. The image information of each color is transmitted to the image forming means 18 of each color in the tandem developing device 120, and a toner image of each color is formed.

The toner image on the black photoconductor 10K, the toner image on the yellow photoconductor 10Y, the toner image on the magenta photoconductor 10M, and the toner image on the cyan photoconductor 10C are sequentially transferred onto the intermediate transfer member 50. (Primary transfer). Then, the toner images of the respective colors are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).
As shown in FIG. 4, the image forming means 18 for each color in the tandem developing device 120 includes a photosensitive member 10, a charger 59 for uniformly charging the photosensitive member 10, and a photosensitive device based on image information of each color. By exposing the body 10 (L in the figure), an exposure device 21 that forms an electrostatic latent image on the photoreceptor 10, and developing the electrostatic latent image using toner of each color, the photoreceptor 10 A developing unit 61 that forms toner images of the respective colors, a transfer charger 62 that transfers the toner images of the respective colors onto the intermediate transfer member 50, a photoconductor cleaning device 63, and a static eliminator 64 are provided.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142a is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145a. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller 142b is rotated to feed out the recording paper on the manual feed tray 52, separated one by one by the separation roller 145b, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.

  Then, the registration roller 49 is rotated in time with the color transfer image formed on the intermediate transfer member 50, and the recording paper is fed between the intermediate transfer member 50 and the secondary transfer device 22, thereby being recorded on the recording paper. A color transfer image is formed. The toner remaining on the intermediate transfer member 50 after the transfer is cleaned by the intermediate transfer member cleaning device 17.

  The recording paper on which the color transfer image is formed is conveyed to the fixing device 25 by the secondary transfer device 22, and the color transfer image is fixed on the recording paper by heat and pressure. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, led to the transfer position again, and after the image is formed on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  The process cartridge according to the present invention is used in the image forming apparatus of the present invention, and integrally supports the image carrier and at least one means selected from a charging device, a developing device, and a cleaning device, and the image forming apparatus main body. It is detachable.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to the Example and comparative example which are illustrated here. In addition, the part in an Example represents a mass part unless there is particular description.

[Production of toner]
A specific preparation example of the toner used for evaluation will be described. The toner used in the present invention is not limited to these examples.
Example 1
<< Manufacture of toner base particles A >>
~ Synthesis of crystalline polyester resin ~
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,300 g of 1,6-alkanediol, 2530 g of fumaric acid, 291 g of trimellitic anhydride, and 4.9 g of hydroquinone were added. After reacting at 5 ° C. for 5 hours, the temperature was raised to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour to obtain [Crystalline Polyester Resin 1]. DSC endothermic peak temperature was 120 ° C., Mn 1500 and Mw 9000. The SP value was 10.8.

-Synthesis of non-crystalline polyester (low molecular polyester) resin-
A 5-liter four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, 229 parts of bisphenol A ethylene oxide side 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, terephthalic acid 208 parts, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 7 hours, further reacted at reduced pressure of 10-15 mmHg for 4 hours, and then 44 parts of trimellitic anhydride was added to the reaction vessel. The mixture was reacted at 180 ° C. and normal pressure for 2 hours to obtain [Amorphous Polyester 1]. [Amorphous Polyester 1] had a number average molecular weight (Mn) of 2,200, a weight average molecular weight (Mw) of 5,800, and a glass transition temperature (Tg) of 55 ° C.

~ Synthesis of polyester prepolymer ~
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate mass% of 1.53%.

~ Synthesis of ketimine ~
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

-Preparation of masterbatch (MB)-
1200 parts of water, carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] 540 parts, [non-crystalline polyester resin 1] 1200 parts, Henschel mixer (made by Mitsui Mining Co., Ltd.) The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

~ Creation of oil phase ~
378 parts of [Non-crystalline polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were placed in a container equipped with a stir bar and a thermometer. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1042.3 parts of a 65% ethyl acetate solution of [Amorphous Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Preparation of crystalline polyester dispersion ~
100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 75 ° C., and then rapidly cooled in an ice water bath at a rate of 27 ° C./min. To this, 500 ml of glass beads (3 mmφ) was added, and pulverized for 10 hours with a batch type sand mill (manufactured by Campehapio) to obtain [Crystalline Polyester Dispersion 1].

~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid, When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) [fine particles Dispersion 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component.

-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give a milky white liquid. Got. This is designated as [Aqueous Phase 1].

-Emulsification / solvent removal-
[Pigment / WAX Dispersion 1] 664 parts, [Prepolymer 1] 109.4 parts, [Crystalline Polyester Dispersion 1] 73.9 parts, [Ketimine Compound 1] 4.6 parts, After mixing for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika), add 1200 parts of [Aqueous Phase 1] to the container, and mix with a TK homomixer at 8,000 rpm for 60 seconds [emulsified slurry 1] was obtained.
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

~ Washing and drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved toner base particles A were obtained with an opening of 75 μm mesh.

(Manufacture of external additives)
The production of the external additives a to q is performed by mixing the primary particles of silica having various average particle diameters described in Table 1 below and the treatment agent with a spray drier and baking the primary particles. Produced by bonding. Further, in order to obtain a sharp particle size distribution as external additive particles, classification treatment was performed with a classifier to prepare coalesced particles having various average particle sizes shown in Table 1.

~ External treatment ~
100 parts by mass of toner base particles A, 2.0 parts by mass of fused silica a in Table 2, 2.0 parts by mass of silica having an average particle diameter of 20 nm, and 0.6 parts by mass of titanium oxide having an average particle diameter of 20 nm The toner was mixed with a Henschel mixer and passed through a sieve having a mesh size of 500 mesh.

(Examples 2 to 6)
As shown in Table 2, toner 2 to toner 6 were obtained in the same manner as in Example 1 except that the fused silica a was changed to fused silica b to fused silica f.
(Examples 7 to 12)
The toner base obtained by changing the mixing time after adding the aqueous phase in the emulsification / desolvation step in the production process of Example 1 [Toner 1] to 90 seconds and changing the aging temperature to 48 ° C. Toner 7 to toner 12 were obtained in the same manner as in Example 1 except that the fused silica g to fused silica 1 were changed to the fused silica a and added to the particles B as shown in Table 2.
(Examples 13 to 17)
The toner base obtained by changing the mixing time after adding the aqueous phase in the emulsification / desolvation step in the production process of Example 1 [Toner 1] to 40 seconds and changing the aging temperature to 42 ° C. Toner 13 to toner 17 were obtained in the same manner as in Example 1 except that the fused silica m to fused silica q were added to particles C in place of the fused silica a as shown in Table 2.

(Example 18)
<< Manufacture of toner base particles D >>
(Preparation of solution or dispersion of toner material)
-Synthesis of non-crystalline polyester (low molecular weight polyester) resin-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize “amorphous polyester 2”.
The obtained “amorphous polyester 2” had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

-Preparation of masterbatch (MB)-
1000 parts by mass of water, 540 parts by mass of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) and 1200 parts by mass of the unmodified polyester were combined with a Henschel mixer (Mitsui Mine). Mixed). The mixture was kneaded with a two roll at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch 2].

~ Preparation of wax dispersion ~
378 parts of “Non-crystalline polyester 2”, 110 parts of carnauba wax, 22 parts of salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.) and 947 parts of ethyl acetate are charged in a reaction vessel equipped with a stirring bar and a thermometer. While stirring, the temperature was raised to 80 [° C.], maintained at 80 [° C.] for 5 [hours], and then cooled to 30 [° C.] over 1 [hour]. Next, 500 parts of [Masterbatch 2] and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 [hour] to obtain [Raw material solution 2].
1324 parts of the obtained [Raw Material Solution 2] was transferred to a reaction vessel and filled with 80 [volume%] of 0.5 mm zirconia beads using an ultraviscomil bead mill (manufactured by IMEX Co., Ltd.). The carbon black and the carnauba wax were dispersed in 3 passes under the conditions of [kg / hour] and the disk peripheral speed of 6 [m / sec] to obtain [Wax Dispersion 2].

~ Preparation of dispersion of toner material ~
Next, 1324 parts of a 65 [mass%] ethyl acetate solution of [amorphous polyester 2] was added to [wax dispersion 2]. A layered inorganic mineral montmorillonite (Clayton APA Southern Clay modified at least partly with a quaternary ammonium salt having a benzyl group) was added to 200 parts of a dispersion obtained by one pass using Ultraviscomyl under the same conditions as above. (Products) 1.0 part was added. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred for 30 minutes to obtain a [toner material dispersion].

-Preparation of aqueous medium phase-
660 parts by mass of water, the above [fine particle dispersion 1], 25 parts by mass, 25 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and ethyl acetate 60 parts by mass were mixed and stirred to obtain a milky white liquid (aqueous phase). When observed with an optical microscope, several hundred μm aggregates were observed. When this aqueous medium phase was stirred at 8000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), it was confirmed by an optical microscope that the aggregates were loosened and could be dispersed into small aggregates of several μm.

~ Emulsification or preparation of dispersion ~
150 parts by mass of the aqueous medium phase is put in a container and stirred at 8000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and 100 parts by mass of the [toner material dispersion] is added thereto. The mixture was mixed for 60 seconds to prepare an emulsified or dispersed liquid (emulsified slurry 2).

~ Removal of organic solvent ~
[Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 2].

~ Washing and drying ~
[Dispersion slurry 2] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 2]. It was.
[Filter cake 2] was dried at 45 ° C. for 48 hours with a circulating drier, and sieved toner base particles D were obtained with a mesh opening of 75 μm.

~ External treatment ~
100 parts by mass of toner base particles D, 2.0 parts by mass of fused silica a in Table 2, 2.0 parts by mass of silica with an average particle diameter of 20 nm, and 0.6 parts by mass of titanium oxide with an average particle diameter of 20 nm Parts were mixed with a Henschel mixer, and passed through a sieve having a mesh size of 500 mesh, whereby toner 18 was obtained.

(Examples 19 to 23)
As shown in Table 2, toner 19 to toner 23 were obtained in the same manner except that the fused silica a in Example 18 was changed to fused silica b to fused silica f.
(Examples 24-29)
The mixing time after adding [Toner Material Dispersion] in the emulsification or dispersion preparation step in the manufacturing process of Example 18 [Toner 18] is changed to 90 seconds, and the aging in the organic solvent removal step is performed. To the toner base particles E obtained by changing the temperature to 48 ° C., as in the combination shown in Table 2, Example 18 except that the fused silica g to fused silica 1 were changed to the fused silica a and added, respectively. In the same manner, toner 24 to toner 29 were obtained.
(Examples 30 to 34)
The mixing time after adding [toner material dispersion] in the emulsification or dispersion preparation step in the manufacturing process of Example 18 [Toner 18] is changed to 40 seconds, and the aging in the organic solvent removal step is performed. As in the combinations shown in Table 2, the toner base particles F obtained by changing the temperature to 42 ° C. were used in the same manner as in Example 2 except that the fused silica m to fused silica q were changed to the fused silica a and added. 18 to obtain toner 30 to toner 34.

(Example 35)
<< Manufacture of toner base particles G >>
(Adjustment of resin emulsion)
The following monomers are mixed uniformly to prepare a monomer mixture.
Styrene monomer 71 parts n-butyl acrylate 25 parts acrylic acid 4 parts The following aqueous solution mixture is placed in a reactor and heated to 70 ° C under stirring. While stirring the liquid temperature at 70 ° C., 5 parts of the monomer mixture and 1% aqueous solution of potassium persulfate were added dropwise simultaneously over 4 hours, and further polymerized at 70 ° C. for 2 hours to obtain a solid content of 50%. A resin emulsion was obtained.
Water 100 parts Nonionic emulsifier (Emulgen 950) 1 part Anionic emulsifier (Neogen R) 1.5 parts

(Toner particle adjustment)
The following mixture was stirred for 2 hours at 25 ° C. using a disper.
20 parts of pigment (carbon black (“Printtex35”; manufactured by Degussa)
DBP oil absorption = 42 ml / 100 g, pH = 9.5)
Charge control agent (E-84, manufactured by Orient Chemical Co., Ltd.) 1 part Anionic emulsifier (Neogen R) 0.5 part Water 310 parts And adjusted to pH 7.0 with ammonia. Further, this dispersion was heated to 90 ° C. and maintained at this temperature for 2 hours to obtain [Dispersion Slurry 3].
[Dispersion Slurry 3] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(2): 10% hydrochloric acid was added to the filter cake of (1) to adjust to pH 2.8, mixed with a TK homomixer (rotation speed 12000 rpm for 10 minutes), and then filtered.
(3): 300 parts of ion-exchanged water was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered twice to obtain [filter cake 3].
[Filtration cake 3] was dried at 45 ° C. for 48 hours with a circulating drier, and sieved with a mesh of 75 μm to obtain toner base particles G.

~ External treatment ~
100 parts by mass of toner base particles G, 2.0 parts by mass of fused silica a in Table 2, 2.0 parts by mass of silica with an average particle diameter of 20 nm, and 0.6 parts by mass of titanium oxide with an average particle diameter of 20 nm The parts were mixed with a Henschel mixer and passed through a sieve having a mesh size of 500 mesh to obtain toner 35.

(Examples 36 to 40)
As shown in Table 2, toner 36 to toner 40 were obtained in the same manner as in Example 35 except that the fused silica a was changed to fused silica b to fused silica f.
(Examples 41 to 46)
It was obtained by changing the stirring temperature after adding the emulsion to the dispersion in the production process of Example 35 [Toner 35] described above to 55 ° C. and changing the holding time after heating at the time of preparing the dispersion slurry to 6 hours. As in the combinations shown in Table 2, the toner base particles H are operated in the same manner as in Example 35 except that the fused silica g to fused silica 1 are added to the fused silica a, and toner 41 to toner 46 are replaced. Obtained.
(Examples 47 to 51)
Toner obtained by changing the stirring temperature after adding the emulsion to the dispersion in the production process of Example 35 [Toner 35] described above to 65 ° C. and changing the heating temperature during preparation of the dispersion slurry to 80 ° C. Toner 47 to toner 51 are obtained in the same manner as in Example 35 except that the fused silica m to fused silica q are changed to fused silica a and added to the base particles I as shown in Table 2. It was.

(Comparative Example 1)
Toner base particle J was prepared by changing the aging temperature in the emulsification / desolvation step in the production process of Example 1 [Toner 1] to 50 ° C. As shown in Table 2, external addition to the toner base particle was performed. A toner 52 was obtained in the same manner as in Example 1 except that the silica silica r (average particle diameter: 120 nm) was used.
(Comparative Example 2)
As shown in Table 2, a toner 53 was obtained in the same manner as in Comparative Example 1 except that the spherical silica r externally added to the toner base particles J was changed to the fused silica a.
(Comparative Example 3)
As shown in Table 2, a toner 54 was obtained in the same manner as in Comparative Example 1 except that the spherical silica r externally added to the toner base particles J was changed to the fused silica c.
(Comparative Example 4)
As shown in Table 2, a toner 55 was obtained in the same manner as in Comparative Example 1 except that the spherical silica r externally added to the toner base particles J was changed to the fused silica e.
(Comparative Example 5)
As shown in Table 2, a toner 56 was obtained in the same manner as in Example 1 except that the fused silica a externally added to the toner base particles A was changed to true spherical silica r.

(Comparative Example 6)
Toner base particles L were prepared by changing the aging temperature in the emulsification / desolvation step in the production process of Example 1 [Toner 1] to 40 ° C. As shown in Table 2, external addition to the toner base particles was performed. A toner 57 was obtained in the same manner as in Example 1 except that the silica silica a was changed to true spherical silica r.
(Comparative Example 7)
As shown in Table 2, a toner 58 was obtained in the same manner as in Comparative Example 6, except that the spherical silica r externally added to the toner base particles L was changed to the fused silica a.
(Comparative Example 8)
As shown in Table 2, a toner 59 was obtained in the same manner as in Comparative Example 6, except that the spherical silica r externally added to the toner base particles L was changed to the fused silica c.
(Comparative Example 9)
As shown in Table 2, a toner 60 was obtained in the same manner as in Comparative Example 6 except that the spherical silica r externally added to the toner base particles L was changed to the fused silica e.
(Comparative Example 10)
As shown in Table 2, a toner 61 was obtained in the same manner as in Example 30, except that the fused silica m externally added to the toner base particles F was changed to true spherical silica r.

[Evaluation item]
(Transfer stability)
After the image area ratio 20% chart is transferred from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before the cleaning is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and is transferred to a Macbeth reflection densitometer RD514 type. Measured and evaluated according to the following criteria.
〔Evaluation criteria〕
A: The difference from the blank is less than 0.005.
(Circle): The difference with a blank is 0.005-0.010.
(Triangle | delta): The difference with a blank is 0.011-0.02.
X: The difference with a blank exceeds 0.02.
◎, ○, and Δ were determined to be acceptable, and × was determined to be unacceptable.

(Filming evaluation method)
1. All toners and devices used for evaluation are left at 25 [° C.] in a 50% environment room for 1 day.
2. All the toner on the PCU of the copier is removed, leaving only the carrier in the developing device.
3. In a developing device having only a carrier, 28 [g] of black toner as a sample is charged, and 400 [g] of a developer having a toner concentration of 7 [%] is created.
4). A developing device is attached to the copying machine body, and only the developing device is idled for 5 [minutes] at a developing sleeve (sleeve forming the surface of the developing roller) at a linear speed of 300 [mm / s].
5. Both the developing sleeve and the photosensitive member are rotated by trailing at a target linear velocity, and the charging potential and the developing bias are adjusted so that the toner on the photosensitive member becomes 0.4 ± 0.05 [mg / cm ² ].
6). Under the above development conditions, the transfer current was adjusted so that the transfer rate was 96 ± 2 [%].
7). Full-page solid images were output continuously at 10,000 [sheets].
8). Sensory evaluation was performed on the image quality of the output image, and the number of white spots due to filming was counted.

The evaluation criteria for filming properties were as follows.
◎: There are few white-out image parts and is quite good. ○: White-out parts are rarely seen. △: White-out parts are conspicuous. ×: There are many white-out parts. ◎, ○, △ are acceptable, and x is unacceptable. Judged.

(Low temperature fixability)
A copying test was performed on type 6200 paper (manufactured by Ricoh) using an apparatus in which a fixing unit of a copying machine MF2200 (manufactured by Ricoh) using a Teflon (registered trademark) roller as a fixing roller was modified.
Specifically, the cold offset temperature (fixing lower limit temperature) was determined by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The lower limit fixing temperature of the conventional low-temperature fixing toner is about 140 ° C.
At this time, the fixing lower limit temperature is ◎ when the temperature is less than 120 ° C, ◯ when the temperature is 120 ° C or more and less than 130 ° C, Δ when the temperature is 130 ° C or more and less than 140 ° C, and × when the temperature is 140 ° C or more. , ◎, ○, Δ were judged as acceptable, and x was judged as unacceptable.

(Storability)
After the toner was stored at 40 ° C. and 70% for 14 days, it was sieved with a 200 mesh sieve for 1 minute, and the residual rate on the wire mesh was measured.
At this time, the residual rate of toner having better storage stability in a high humidity environment is smaller.
The storage stability in a high humidity environment is ◎ when the residual rate is less than 0.1%, ◯ between 0.1% and less than 0.5%, △ between 0.5% and less than 1%, The case of 1% or more was judged as x, ◎, ○, Δ were judged as acceptable, and x was judged as unacceptable.

The evaluation results of manufactured toner 1 to toner 61 are shown in Table 3.

DESCRIPTION OF SYMBOLS 10 Photoconductor 10K Black photoconductor 10Y Yellow photoconductor 10M Magenta photoconductor 10C Cyan photoconductor 14, 15, 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer Device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing Belt 42K, 42Y, 42M, 42C Developer container 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Developer roller 45K Black developer 45Y Yellow developer 45M Magenta developer 45C Cyan Present Device 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Manual feed tray 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 59 Charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Recording paper 100A, 100B, 100C Image forming device 110 Belt type fixing device 120 Tandem type developer 130 Document table 142a, 142b Paper feed roller 143 Paper bank 144 Paper feed cassette 145a, 145b Separating roller 146 Feeding path 147 Conveying roller 148 Feeding path 150 Copier main body 200 Feeding table 300 Scanner 400 Automatic document feeder

Japanese Patent No. 03030741 JP 2000-112174 A JP 2001-201891 A JP 2001-235894 A Japanese Patent Laid-Open No. 3-100161 Patent No. 033828013 JP-A-9-319134 Japanese Patent No. 03056122 JP-A-8-176310 Japanese Patent No. 3684074 JP 2010-224502 A

Claims (10)

An electrostatic charge image developing toner having inorganic fine particles as external additives on the surface of toner base particles having at least a binder resin and a release agent, wherein the toner base particles have a BET specific surface area of 2.5 m ² / g to 5.0 m ² / g, and the inorganic fine particles contain inorganic fine particles (A) in which at least a plurality of primary particles are combined to form secondary particles. Toner. The toner according to claim 1, wherein the BET specific surface area of the toner base particles is 3.5m ² /g~5.0m ² / g.   When the particle diameter of the 50% measured from the small particle side of the secondary particle diameter Db of the inorganic fine particles (A) is Db50 and the particle diameter of the 10% measured from the small particle side is Db10, Db50 / Db10 is The electrostatic image developing toner according to claim 1, wherein the toner is 1.20 or less.   When the secondary particle diameter of the inorganic fine particles (A) is Db, the average primary particle diameter of a plurality of primary particles forming the secondary particles is Da, and the adhesion degree G = Db / Da, the adhesion degree The toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein an average value of G is 1.5 to 4.0.   5. The toner for developing an electrostatic charge image according to claim 1, wherein the inorganic fine particles (A) contain 10% by number or less of particles having an adhesion degree G of less than 1.3. 6.   6. The electrostatic image developing toner according to claim 1, wherein the inorganic fine particles (A) have an average secondary particle diameter Dba in the range of 80 nm to 200 nm.   The toner for developing an electrostatic charge image according to claim 1, wherein the toner is granulated in an aqueous medium.   In the toner, an oily phase obtained by dissolving or dispersing a toner material containing at least a polyester resin, a colorant, and a release agent in an organic solvent is dispersed in an aqueous medium to obtain an emulsified dispersion, and the emulsified dispersion is obtained. 8. The electrostatic image developing toner according to claim 1, wherein the toner is obtained by removing an organic solvent from the liquid.   A two-component developer containing the electrostatic image developing toner according to claim 1.   An image forming apparatus using the electrostatic image developing toner according to claim 1.